Synthesis and reactivity of (LRe(NO)(CO)(NCO))/sup +/ (L = 1,4,7-triazacyclononane). Kinetics and mechanisms of its formation and transformation to (LRe(NO)(CO)X)/sup n+/ (X = NH/sub 3/, Cl, HCO/sub 2//sup -/, CF/sub 3/SO/sub 3//sup -/) and other species. Crystal structure of (LRe(NO)(CO)(NH/sub 3/))Br/sub 2/

The complex (LRe(NO)(CO)(NCO))(BF/sub 4/) (1) has been synthesized from (LRe(NO)(CO)/sub 2/)(BF/sub 4/)/sub 2/ (L = 1,4,7-triazacyclononane, C/sub 6/H/sub 15/N/sub 3/) in methanol with a variety of nucleophiles such as N/sub 2/H/sub 4/ x H/sub 2/O, H/sub 2/NNH(CH/sub 3/), H/sub 2/NN(CH/sub 3/)/sub 2/, H/sub 2/NOH, and N/sub 3//sup -/. The kinetics and mechanisms of the formation of 1 have been investigated. A general mechanisms for these reactions is proposed: nucleophilic attack at a coordinated carbonyl produces carbazoyl intermediates when hydrazine or its N-methylated derivatives are reactants. In the rate-determining step, NH/sub 3/, NH/sub 2/(CH/sub 3/), or NH(CH/sub 3/)/sub 2/ is then cleaved off and fast rearrangement to the N-coordinated isocyanate occurs. 1 undergoes a series of reactions at the coordinated isocyanate ligand; e.g. concentrated HBr reacts in CH/sub 3/OH with 1 to produce (LRe(NO)(CO)(NH/sub 3/))Br/sub 2/ (3), the crystal structure of which has been determined by X-ray crystallography. The kinetics and mechanisms of the reaction of 1 with H/sup +/ to produce 3 and CO/sub 2/ have been investigated. 3 is electrochemically or chemically oxidized to paramagnetic (LRe(NO)(CO)(NH/sub 3/))Br/sub 3/. The reaction of 1 with concentrated formic acid, trifluoromethanesulfonic acid and iodide anion were investigated, and the products of the reactionsmore » are reported. Spectroscopic properties (/sup 1/H and /sup 13/C NMR, vis, ir) are reported for all compounds. 38 references, 5 figures, 6 tables.« less